Process and apparatus for the rectification of crude petroleum and other volatile liquids.



E. GUILLAUME. V PROCESS AND APPARATUS FOR THE BBCTIFIGATION 0F CRUDEPETROLEUM AND OTHER VOLATILE LIQUIDS;- APPLIOATION IIIiED JULYS, 1908.

996,081, Patented June 27, 1911.

To all whom it may concem:

- other Volatile Liquids, (for which a French UNITED STATES PATENToFFIoE.

EMILE summons, 61 rams. Rance."

PROCESS AND nrisnn'rus FOR THE nucrrrronrrouor CRUDE. PETROLEUM ANDornnn VOLATILE'LIQUIDVS.

s ecification 1 Letters Patent. Patented June 27,. 191 1.

Application filed July 9,,1908. Serial No. 442,764.

Be it known that I, EMILE GUILLAUME,

citizen of France,'residing at Paris, in the said Republic, haveinvented new and useful Improvements in Processes and Apparatus for theRectification of Crude Petroleum. and

patent has been filed July 19, 1907,) of which the following is aspecification;

The present invention relates to a process of and apparatus for therectification of crude petroleum and like liquids composed of variouscomponents having maxima of volatilizationat different temperatures, the

object beiilg to obtain the fractional distillation of the liquid into anumber of separate portions, in each of which portions the substancescontained will volatilize atas nearly as possible the same temperature.

The process of this invention has for its purpose the separation andsimultaneous rectification of each ofa plurality. of volatile portionsof the petroleum products and. is

adapted for the treatment'of the crude volatile oils produced bypreviousdistillation of crude petroleum ds well as for the direct treatment ofcrude petroleum. The process is not particularly. intended for thedistillation and rectification of the less volatile petroleum products,such as par'aflin and the like, but said process is applicable to therectification of the crude more volatile oily products formedin thefirst phase-of the ordinary distillation of crude petroleum,distillation of petroleum being usually stopped before the heavy oilspass into the distillate. The crude volatile oils thus obtained do notcontain anyv substantial amount of paraffin oil (orlot-her heavyresidues) when they are 1 finally submitted to rectification under theThe process may also ti)? crude petroleum itself is used instead of the3 present process. applied directly. to crude petroleum.

crude volatile oils produced by a'preliminary distillation of crudepetroleum, by fat p lowing the present mode of operation, not "only can.the said volatile oily products be separated from the petroleum, butbesides,

they may be respectively rectified, this rectification being separatelyalthough simultaneously eflected, for each product of equal density. Theundistilled portion off-the petroleum recovered may also be perfectlypurified of all the volatile oils. which it contains,

' whilestill containing the heavier-"oily prod-' acts, such as heai'yburning oils and other heavier residues,-which may be treated separatelyby ordinary means. If desired, the operation may be extended to extractand rectify still heavier volatile petroleum oils distilling column,operated in a methodical and continuous manner and comprising as manysuperlmposed stages as there are distinct products to-be separated andrectifiedi-n-the apparatus (with the exception of the residuary'productissuing from the base .Of-

the column), and each of thesestages should contain a suflicient numberof plates to insure that the more volatile products in the liquid whichpasses downward through each stage should be' completely distilledtherefrom, so thatsuch products shall not be found in the stageimmediately below. The still should be provided with means at or nearits top for introducing the material to be treated, which may be crudepetroleum or crude volatile products formed by a preliminarydistillationof petroleum. The still should also be provided with a plurality ofvapor outlets along its sides, each such vapor outlet. corresponding to.a distinct stage in the distilling operation taking placein the column.There should also be a .vapor outlet at the top. For each of thesevapor, outlets should be provided a distinct rectifying column, eachsuch rectifying column containing a number of plates of the ordinarytypes and being adapted to secure a rectification of the vapor enteringthe column and coming from a discrete stage in the primary column still.The roduct from each rectifying column should be purified or rectifiedtherein from the heavier products accompanying the vapors coming fromthe primary column.

Iroper connections should be made to allow mary column still at the topof the stage immediately below the one from which the vapors passing tosuch rectifying column were drawn.

The process of the present case consists,

briefly stated, in passing the material'to be treated which may be,asstated, crude petroleum or a crude volatile product therefrom, downthrough a primary distilling column operating in a plurality. ofdiscrete stages, and in withdrawing vapor from the top of each suchstages and submitting it to treatment in a rectifying column, theheavier products separated in each such rectifying column being returnedto the primary still at astage next below that from which the vaporcame. p

An apparatus designed-for carrying. this process into efi'ect isillustrated more or less diagrammatically in the accompanying drawing,which shows, by way of example, a distilling apparatus adapted for thedistillation 'or separation of crude petroleum or petroleum productsinto seven distinct lots or fractional portions. tration, which islargely diagrammatic, for the sake of clearness, certain pipes or conduits carrying liquid petroleum products have been extra-marked with anarrow and P, certain other conduits carrying vapor have beenextra-marked with a V and an arrow and certain other conduits carryingcooling water have been extra-marked with a W and an arrow.

The primary column still is lettered A and is divided into a number ofsuperimposed stages marked respectively a a, a a*,.a and a. The severalrectifying columns are marked B, that for the top stagebeing-superimposed on the top of the primary column A and marked. Bwhile the others are marked B B, B, B and B respectively. The severalcondensers are marked 0 c", c, a, c and 0". The inlet pipe 1 furnishespetroleum to tank or cistern 2 whence it flows through pipe 3 controlledby valve 5 into preheater or heat interchanger 4, this preheatercontaining the usual tube-nest, The heated oil is delivered through 6past 7 into the'top of the still. The exhausted residual liquid from thebase of the still passes through 1' into the base of the heater a,furnished with steam through Z, Z being provided for exit of condensedsteam. The vapor produced in this heater passes through 20 and 21 intothe base of the column still. Residual liquid from the heater goesthrough 13 past valve 14 into and through the preheater (4) passingthence through 15 into cooler 16 whence fit emerges through 17. Coolingwater is 1 to this cooler through 18 and emerges ough 19. The vaporsproduced in the top stage a of the primary still passdirectly-upwardgiifito B. The vapors prosupplied- In this illus-'through 8 and 0'' into B and those from the succeeding lower stages passrespectively through connections 9, 10, 11 and 12 and 0 0 ,0 and 0" intoB B, B and B". The vapors from the rectifying columns B etc., passrespectively through e e 6 e, e and a into condensers 0 c c 0', c andp,whilea portion of the condensed heavier products flow back through 6 2'2' i 2' and i into the top of the respective rectifying columns. Each ofthe condensers (0, 0 etc.) .is provided with an adjacent cooler (1' 77etc) communication being respectively through f f etc. Each of thesecoolers is provided with a waterjnlet (w, u'-, etc.) and with a wateroutlet 11 '0 etc.)

and with adelivery outlet g 1 etc.) provided with appropriate cocks (7Lh etc.).

Each of the condensers c 0 etc., is provided with a water outlet of, 02etc. The rectifying columns are provided respectively with thermometers,all being marked 22.

In the use of this apparatus, suppose that the material to be treated iscomposed of several components, A, A A A", the component A being themost volatile, and the boiling temperature of each o-f-the componentsbeing, respectively, t, t-, t t. The material in question is introducedat the. top of the distilling column through 6 and the entire componentA which is themost volatile, will be completely distilled on the platesof the section a of the column,

so that it will be completely eliminated from distilled on the" platesof the section a so that it will be entirely eliminated from the liquidwhich-passes downward below the va-.

por outlet 9, and so on, for all the other components, so that nothingenters the heater a but'the less volatile component A. The heatnecessary to eifect these successive distillations is furnishedefliciently and entirely by vaporsformedin the heater a7, which isheated sufiiciently for that urpose. The residuary product which issuesom the base of the distilling column A through the. tube 2" enters thedevice a below the casing which incloses the same and traverses thetubes of the tube nest within the casing and.

issues therefrom-at the upper part through the tube 13. The residuaryproduct is allowed to pass. freely through the tube 13, cook 14 beingalways wide open in normal operation. This cock is only used at the endof an operation, itsclosing then preventing insufficiently exhaustedproducts, which may pass to the-base of the column A, passing throughtube 13 into cooler 16 which should normally only receive exhaustedresiduary products. When in normal operation the residuary productpasses through tube 13 bottom upward, and the condensed water exhauststhrough Z at the lower part of the casing. Any desired temperature maybe,

used.

It should be noted that the distillation of petroleum products requiresmuch less heat than the distillation of other liquids, such asalcohollfor example. It is well known that alcohol distilling andrectifying columns, operating continuously, are readily heated by meansof a single heating member placed at their base, and it will beevident,c fortiom' that the single heating device a at. the base of thedistilling column A, will efficiently heat the column. Heating device afurnishes all the vapor necessary to the vaporization of all thefractional portionsto be separated in the column A, from the portioncomprising the residuary product. The vapor issuing from the heater aand entering the base of the column A through 20 operates, first of all,in the distillation of the oily product intended to constitute the sixthfractional portion, vapors being diverted through the tube 0, from upperpart of the stage or division at of the column A.

In the same way division a istraversed by all the remaining Vapor, thatis to say, by all that is necessary for the distillation of the nextfractional portion. The vapors constituting the fifth fractional portionare a thermometer 23, placed at the base of the diverted throughll andtube 0 from the upper part of the division a of the distilling column A,and so on for each of the successive fractional portions,the result ofwhich is that the division a is only traversed by the vapor necessaryfor the distillation of the vapors constituting the first orlowestboiling fractional portion.

It. will be seen from the above description that the process iscarriedon with a small expenditure of heat.

The heating system is regulated in accordance with the indicationsfurnished by vthe column A, which should indicate a predetermined normaltemperature. at the time the apparatus is set to work, corresponding tothe nature of the products which are to'be treated therein. If thetemperature indicated by the thermometer 23 rises above thispredetermined temperature, it shows that the vapors at the base of thecolumn A contain too great a quantity of the less volatile products, andthat, therefore, the operation of the heater (1 is too active: it is.therefore, necessary'i tgodiminish the intensity of the heat in thel'latter. If on the contrary the indicated temperature falls below thepredering apparatus for each let 8.

termined temperature, the intensity of the heat must be increased.

The crude, petroleum or crude petroleum distillate flowing into thesystem through the pipe 1, fills the cistern 2, and passes through thepipe 3, into the heat interchanger 4, the quantity passing being con-.trolled by the cock 5. The material thence passesthrough the pipe 6 tothe top of the distilling column A. The pipe 6 is not .throttled andthis allows vapors'of volatile components which have been vaporized inthe course of the heating of the material in its passage through theheat interchanger 4 to escape with the liquid into the distillationcolumn A without passing any regulating valve. The portion a of thecolumn A comprised between the end 7 of the admission pipe. (5 for thecrude materialand the end 8 of the outlet pipe 0 for the vapors whichform the second fractional portion, corresponds tothe first stage of.the distillation column through'which the petroleum passes indescending. The vapors produced by the distillation in the first stage(Z that is to say, those which are intended to form the first fractionalportion, pass directly, as in-.

dicated by the arrow 0 into the bottom of the first rectifying column Ballowing the less'volatile essences which have been carried over withthe said vapors to fall back directly into the distillation column A andto pass on downward with the other portions in that column. The vaporsfor forming the first portion, thus concentrated by means of a cook it?and may pass through a supplementary refrigerator, if desired, to thetesting apparatus (not shown) which serves as a control in securing thecorrect.

density for this first portion. A connecting pipe 2' permits thereturnto the top of the rectifying column B of a part of the liquidcondensed in the condenser 0 The supplemental refrigerators and testanydesired type.

The most volatile bodies forming the first fractional portion of theproduct are completely. vaporized and eliminated by methodicaldist-illationbefore the material under treatment in flowing down throughthe portion may be of still has reached the level of the vapor outandhas been described with respect to the first stage, the bodies intendedto form the second distillation portionand to be drawn through theoutlet .pipe 0 are therem vaporized and completely eliminated before thematerial'under treatment has reached the level of the vapor outlet 9through which the vapor to form the third fractional portion passes. Thesame explanation applies to the parts a a a andol comprised,respectively, between the fvapor outlets 9 .and 10, 10 and 11, 1 1 and12, and 12 and the bottom of the column A, in which parts the bodiesforming the third, fourth, fifth .and sixth fractional portions arevaporized and separated and respectively drawn out through the outletpipes 0 0 0 and 0.

B B, B", B and B are concentration or rectifying columns for the second,third,

fourth, fifth and sixth fractional portions,

respectively. The vapors forming these and refrigerators 1' 1' portionspass, respectively, through the pipes e, e, e, 0" and e, the condensers0;, 0, 0 ,0 and c, the plpes f f f, f and f 1", r and 11, and flow out,respectively, through the pipes g 9 g; 9 and g, and the cocks 72?, h, h,h, and h. Finally, the less volatile products which flow back from theserespective columns pass again into the distillation column through thepipes, Z Z Z, l and l, and the connecting pipes i 2', i i and z', permitthe return to the top of each rectifying col-' umn B B, B", .B and B'ofapart of the liquid condensed in the condensers 0 o, a, c and c. Thepart a below the vapor outlet 12 forms the lowest stage of thedistilling column A, and it is in this part that the sixth fractionalportion is vaporized,

-said VH-POI lZGd fIiICtlOII passing out at 12 through the outlet pipe0. The seventh or residual fractional portion consists of the hotpetroleum residues which pass out by the pipe-13 from the boiler a andpastthe "cock 14, which is wide open, into the tubular partof the heatinterchanger gt, after which these products pass through the pipe 15 to.

the cooler 16 and finally fiow-out, suitably cooled, through pipe 17.The cooling water circulates through the pipe 18, the tubular part ofthe refrigerator 16, and the pipe.

- 19,--in thedirection indicated by the arserving thus -ip distil thevapors forming the sixth portio" (the vapor forming the sixth portionpassing off by the pipe 0) the fifth stage a is traversed in turn by allthe remaining vapor, that is to say, all that is necessary for thevaporization of the first five fractionalportions; in the same mannerthevapor forming the fifth lot having been drawn off by the pipe 0 at thelevel of the fifth stage, the plates at the fourth stage a are traversedonly by the vapors necessary for vaporization of the first fourfractional portions; and for the remaining stages the procedure is thesame until the first stage a is reached through which only as. much ofthe heating vapor flows as is necessary for the distillation of thefirst portio The above explanation shows that, in the new process, theheat necessary for the complete and successive distillation in a simul-'taneous and continuous manner of the six fractional portions isconsiderably aug-j mented without the necessity of correspondinglyincreasing the totalheating. Similarly the heat necessary for thedistillation of the first five portions all comes into play- 'stantpercentage of alcohol from the production of concentrated alcohols bythe distillation of wine. Thermometers, 22,- arranged at the base ofeach of the concentration columns make it" possible to control thetemperature of the vaporized "'essences entering these columns andconsequently to control the cooks b b 6, 6 b", which regulate the accessof the said vapors into the concentration columns B-, B B, B and B; Itwill thus be seen that by the combined use of the cooks k and bcontrolling, respectively,

" the outflow of the bodies forming thefirst portion, and the entry ofthe bodies forma ing the second portion, into the concentration column Band then respectively of the cooks k and b, k and I), k and b, 71 and b,and, finally, of the coclck and the degree of heating in the'boiler a itis possible to maintain constant the temperatures ofthe vapors enteringat the base of each concentration column respectively, and thus toinsure the permanence of the composition of the vapors. A

The following description will illustrate how the operation of theprocess in question can be practically carried'out. Throughout thedescription temperatures are referred to in thermometric degrees of thecentigrade system. Suppose, for the sake of example,

that it is a question ofseparating into six 'distinct fractions theseveral components contained in a crude petroleum and divided asfollows: Product A comprising 1.5% by volume of the raw material will bean oil weighing 630 grams per liter and boiling at 45. Product Acomprising 2% by volume of the raw material will be an oil weighing 650grams per liter and boiling at 65 Product A comprising 2.5% by volume ofthe raw material will be an oil weighing 680 grams per liter and boilingat 85.-

Product A comprising 3% by volume of the raw material will be an oilweighing 695 grams per liter and boiling at 95. Product A ,comprising4%by volume of the raw material will be an oil weighing 720 grams perliter and boiling at 120. Product A comprising 2% by volume of the rawmaterial will be anoil weighing 760 grams per liter and boiling at 140.The crude material,'the feed of which is regulated by the cock 5 placedbetween the tank 2 and the heat exchanger 4, traverses this latter, thenpasses through the tube 6'to the upper plate of the distilling column A.Simultaneously steam under pressure, being, if necessary, superheated tothe necessary temperature, is brought through Z into the heating devicea, the condensation issuing through Z. The column A being thus put intooperation and the cocks h it being closed, and also the cooks b .'..b,.one' commences by regulating the outlet cock h of column B, by

opening the said cock progressively until the density of the'liquidflowing at the.cor responding gage, which should always be composed ofthe productiA slightly 'exceeds the value 630. As soon as this value ispassed, which proves that alittle of the product A has reached the gageappropriated to product A, the opening of the cock k isreduced to adegree strictly necessary to keep the density at 630. This having beendone, one opens wide the cock 6 which causes the withdrawal ofthecrectified prod uct corresponding to andfeeding the rectifying columnB keeping closed the outlet cock'h during the time necessary for theproper rectification; then the cock /L2 is opened very little at first,to cause the least possible flow at the correspondinggage, so

i as to make sure that the density of the issuing product is no longer630; indeed, if this density was still 630, this would prove that theheating of the distilling column A is not sufficient to distil theproduct A completely on the series of plates which constitute the stagea, comprised between the inlet 7 of the crude material and the vaporoutlet 8 of the withdrawalportion which feeds the" column B'-' In thiscase, one would greatly increase the heat in the boiler a, and wouldagain-regulate the cock ll until 'the density d inthe outletgage of theessence .A was no longer 630. One then operates 'the regulation of cockk proceeding in the same manner as with cock k so as to obtain themaximum flow, of product A of density 650, at-

the corresponding outlet gage. When the operation of column B has beenstarted,

column B is set in operation exactly as was done with column B, and, ifnecessary, the heat of the distilling column A is increased so that theproduct A may be completely distilled on the series of plates of thestage a comprised between the vapor outlets 8 cessive operation of therectifying columns B, B? and B, and the respective adjustments of thecooks b b", b and b. For the adjustment of cock'b one first makes surethat product A, density 760, has been completely eliminated from theresiduary petroleum at its issue from the apparatus, it' beingunderstood that if the elimination of any one of the products in thestage appropriated to its distillation is insufficient, the heat isincreased until this elimination is complete. The petroleum issuing atthe base of the apparatus will thus be perfectly purifiedof the volatileproducts whichit contains and which it is desired to produce, but it"still will contain the whole of the products less volatile than thelatter. Strictly speaking, the process could be extended up to theextraction and rectification of kerosene and the like heavy burningoils, so as to leave in the residuary product issuing at the base of thedistilling column A:only the heaviest residue.- But considering the veryhigh degree of temperature, and to avoid the possibility of theformation 'of solid products, it is preferable not to push thedistillation of the crude petroleum too far in the apparatus. To sum up,by operating thus and in the case of the example chosen,

there will be obtained from the raw material exactly 1.5% by volume of aproduct weighing 630 grams per liter, (product A part of the columns B,B B and between 140160 degrees for the thermometer placed at the lowerstage a of the distilling column.

It will be advantageous to control the heating of the boiler a by meansof a regulator, several forms of such regulators being of course knownfor use with water. But it will be necessary to replace the watergenerally employed to actuate the floats of said regulators, by theresidual petroleum coming for example from: the distillation column A,that is to say, by petroleum having a high temperature of vaporizationin order to avoid the production of any ebullition in the saidregulator, and to prevent tli'e entry of water into the distillationcolumn. same would be the case if automatic regulators were'being usedto control the entry of water of refrigeration circulating through thepipes u, 12 m a, o, m, such regulators being already well known in theiraction with water. I

Finally, the arrows marked on the draw- 'ing indicate the direction ofcirculation;

that is to say, the arrows P show the direction of flow of the.petroleum or liquid bodies, the arrow G shows the flow of thenon-condensable. gases, escapin through the pipes p p, from the reigerators 7- 1", the arrow V shows the direction of flow of thevaporized petroleum products, the arrows W- show the direction of theflow of the water, and finally the arrows Z and Z show the entrance ofthe heating steam for the boiler a, and the outlet for the correspondingcondensed water. Having now particularly described and ascertained thenature of my said invention and in what manner the same is to beperformed, I declare that what I claim is 1. An improved process for theseparation.

and rectification of petroleum and all'liquids composed of diverseproducts capable of volatilization at diflerent temperatures, whichconsists in introducing the liquid at the top of a main continuousdistilling column, having as many stages as there are products to beseparated, withdrawing from the top of The each of these stages thevaporized products which traverse it and feeding each of them into thelower-part of a rectifying column, extracting the rectified product fromthe top of the upper part of the main rectifying column and. returningthe less volatile products, which sink in the said column and issue atits lower part to the top of the corresponding stage of the distillingcolumn, and withdrawing the residua-ry products of the operation fromthe base of't-he saidmaindistilling column, substantially as described.

2. An apparatus for distilling petroleum and the like comprising acontinuous distilling column, means for feeding the products to betreated to its upper part, means for withdrawing from its lower part theresiduary product of the operation, and' means for withdrawing from thesaid distilling column at intermediate points the distinct products tobe separated and rectified in the apparatus, the said column having atthese intermediate points a number of plates suflicient to assure thecomplete distillation of the more volatile products contained inthe'liquid which traverses the said plates, and a plurality ofsupplemental rectifying columns having their lower ends connected tosaid main column at said intermediate points.

3. An apparatus for distilling petroleum and the like, comprising adistilling column consisting of a plurality of, superimposed distillingportions, a plurality of rectifying columns operatively associated withsaid distilling portions, a conduit extending between each distillingportion and its associated- EMILE GUILLAUME.

Witnesses J ULES FAYOLLET, Ema TICHON.

